US5166030A - Electrostatic image-developing toner containing a quaternary ammonium charge controlling agent - Google Patents
Electrostatic image-developing toner containing a quaternary ammonium charge controlling agent Download PDFInfo
- Publication number
- US5166030A US5166030A US07/757,211 US75721191A US5166030A US 5166030 A US5166030 A US 5166030A US 75721191 A US75721191 A US 75721191A US 5166030 A US5166030 A US 5166030A
- Authority
- US
- United States
- Prior art keywords
- group
- electrostatic image
- developing toner
- atom
- toner according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 125000001453 quaternary ammonium group Chemical group 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000003086 colorant Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- -1 nitro-substituted benzyl group Chemical group 0.000 claims description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- XTEGVFVZDVNBPF-UHFFFAOYSA-L naphthalene-1,5-disulfonate(2-) Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1S([O-])(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-L 0.000 claims 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09758—Organic compounds comprising a heterocyclic ring
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/0975—Organic compounds anionic
Definitions
- the present invention relates to an electrostatic image-developing toner useful for e.g. electrophotographic copying machines.
- a developer useful for e.g. electrophotographic copying machines is first deposited on an image support such as a photoreceptor having an electrostatic image formed thereon. Then, it is transferred in a transfer step from the photoreceptor to a transfer paper and then fixed on a copy sheet in a fixing step.
- a two component developer comprising a carrier and a toner, and an one component developer (a magnetic toner) which requires no carrier, are known for this purpose.
- a Nigrosine dye As an agent for imparting electric charge to a developer, a Nigrosine dye, a charge controlling agent such as a quaternary ammonium salt or a coating agent for carrier, has been known.
- a charge controlling agent such as a quaternary ammonium salt or a coating agent for carrier.
- Japanese Unexamined Patent Publications No. 119364/1982 (which corresponds to U.S. Pat. No. 4,338,390), No. 169857/1985 and No. 54/1989 (which corresponds to EP 284000A) disclose quaternary ammonium salts as charge controlling agents.
- the present inventors have conducted extensive researches to present an electrostatic image-developing toner of high quality which is less likely to bring about copy staining even when time passes. As a result, they have found it possible to solve such problems by incorporating a compound having a certain specific structure into the toner.
- the present invention has been accomplished on the basis of this discovery.
- the present invention provides an electrostatic image-developing toner comprising at least a resin and a colorant, which contains at least one member selected from the group consisting of compounds of the following formulas (I) and (II): ##STR3## wherein each of R 1 , R 2 , Ar 1 and Ar 2 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, and A is (B)(SO 3 .sup. ⁇ ) 2 or MX 6 2 ⁇ ,
- B is ##STR4## (wherein each of R 3 and R 4 is a hydrogen atom, an alkyl group, a hydroxyl group or an amino group), M is a titanium atom, a zirconium atom or a silicon atom, and X is a fluorine atom, a chlorine atom or a bromine atom.
- FIG. 1 is a graph showing the relation between the amount of a charge-controlling agent incorporated and the quantity of charge imparted to a toner, wherein symbol represents Example 25, symbol ⁇ represents Example 26, and represents Comparative Example 2.
- the electrostatic image-developing toner of the present invention is characterized in that it contains at least one member selected from the group consisting of compounds of the above formulas (I) and (II).
- each of R 1 and R 2 may be an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group; an aralkyl group such as a benzyl group; or a substituted aralkyl group such as a lower alkyl-substituted benzyl group, a nitro-substituted benzyl group or
- a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group or a substituted benzyl group is preferred.
- the sum of the carbon members of R 1 and R 2 is preferably at least 13, more preferably at least 19, most preferably at least 30.
- Each of Ar 1 and Ar 2 which are independent from each other, is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group; an aralkyl group such as a benzyl group; or a substituted aralkyl group such as a lower alkyl-substituted benzyl group, a nitro
- a heptyl group is particularly preferred, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group or a substituted benzyl group.
- the sum of the carbon numbers of Ar 1 and Ar 2 is preferably at least 13, more preferably at least 19, and most preferably at least 30.
- Each of R 3 and R 4 is a hydrogen atom, an alkyl group, a hydroxyl group or an amino group. Particularly preferred is a hydrogen atom, a hydroxyl group or an amino group.
- M is a titanium atom, a zirconium atom or a silicon atom. Particularly preferred is a titanium atom or a zirconium atom.
- X is a fluorine atom, a chlorine atom or a bromine atom. Particularly preferred is a fluorine atom.
- a compound of the formula (I) or (II) can be used for the present invention irrespective of the process for its production. However, an example of a specific process will be described below.
- the compound of the formula (I) can usually be obtained by reacting e.g. a halogenated quaternary ammonium salt of the following formula (IV): ##STR11## wherein R 1 and R 2 are as defined above with respect to the formula (I), and Z.sup. ⁇ is a halogen atom such as chlorine or bromine, with a compound of the following formula (V) or (VI) in water or in an alcohol under heating to a temperature of about 70° C.
- B, M and X are as defined above with respect to the formula (I), and Y is an alkali metal such as sodium or potassium.
- the cation component in the formula (II) can be prepared usually by reacting e.g. a halogenated compound of the following formula (VII):
- Ar' is the same as Ar 1 and Ar 2 in the formula (II), and Y is a halogen atom such as chlorine or bromine, with triethylenediamine in an organic solvent inert to the reaction such as a dimethyl formamide or N-methylpyrrolidone under heating to a temperature of about 70° C. for a period of e.g. 24 hours.
- Y is a halogen atom such as chlorine or bromine
- the resin for the toner of the present invention may be selected from a wide range including known resins.
- a styrene resin a homopolymer or a copolymer of styrene or a substituted styrene
- polystyrene chloropolystyrene, poly- ⁇ -methyl styrene, a styrene-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-butadiene copolymer, a styrene-vinyl chloride copolymer, a styrene-vinyl acetate copolymer, a styrene-maleic acid copolymer, a styrene-acrylate copolymer (such as a styrene-methyl acrylate copolymer, a styrene-e
- These resins may be used alone or in combination as a mixture of two or more of them.
- the content of the compound of the formula (I) or (II) in the toner is preferably from 0.1 to 20 parts by weight, more preferably from 0.2 to 10 parts by weight, per 100 parts by weight of the resin.
- the colorant to be used in the present invention is not particularly limited so long as it is the one which has been commonly employed.
- carbon black may, for example, be used.
- the compound of the formula (I) or (II) is usually white and thus may be incorporated to a colored toner such as a blue, red or yellow toner.
- a colorant composed of a dye or pigment having the corresponding color is employed.
- the content of the colorant is preferably from 3 to 20 parts by weight, per 100 parts by weight of resin.
- charge-controlling agents including known agents such as Nigrosine dyes, quaternary ammonium salts and polyamine resins may be incorporated to the toner of the present invention.
- an additive such as a low molecular weight olefine polymer or fine powder silica may be incorporated in order to improve the fixing property or flowability, as a constituting component of the toner of the present invention.
- the toner may be prepared by a method which comprises kneading the above mentioned respective components by e.g. a kneader, followed, by, cooling, and then by pulverization and classification.
- the toner of the present invention may be applied not only to a two component developer but also to a so-called one component developer (a magnetic toner) such as a capsulated toner, a polymer toner or a magnetite-containing toner.
- the average particle size of the toner is preferably from 5 to 20 ⁇ m.
- the carrier to be mixed with the toner of the present invention to form a developer is preferably a ferrite or magnetite carrier having an average particle size of from 10 to 200 ⁇ m.
- a so-called coating carrier having a fluorine resin coated for the purpose of improving the durability for continuous use may also be used.
- other known carriers including iron powder may also be employed.
- Such a carrier is used preferably in an amount of from 5 to 100 parts by weight per part by weight of the toner.
- the above materials were blended and kneaded, followed by pulverization and classification to obtain a black toner having an average particle size of 11 ⁇ m.
- Example 1 the operation was conducted in the same manner as in Example 1 except that a compound specified in the following Table 1 was used in an amount specified in Table 1 instead of 2 parts of compound (1), whereby a clear copy was obtained as in Example 1.
- a developer was prepared in the same manner as in Example 1 except that compound (1) was not used as the material, and it was used for copying, whereby a copy of poor copy quality with substantial fogging was obtained.
- compound (12) was blended and kneaded in an amount of 0.5 part, 1 part or 2 parts, followed by pulverization and classification to obtain a black toner having an average particle size of 10 ⁇ m.
- a developer was prepared in the same manner as in Example 25 except that compound (29) was used instead of compound (12) as the charge-controlling agent, and the quantity of charge imparted thereto was measured by a blow off method, whereby the characteristic as shown in FIG. 1 was obtained.
- a developer was prepared in the same manner as in Example 25 except that compound (A) ##STR12## was used instead of compound (12), and the quantity of charge imparted thereto was measured by a blow off method, whereby the characteristic as shown in FIG. 1 was obtained.
- styrene acrylate resin SA-302, tradename, Nippon Carbide K.K.
- compound (12) 1 part was mixed by a mixer to let it deposit on the polymer surface to obtain a pseudo-toner.
- This pseudo-toner was shaken with an iron powder carrier for 30 minutes at a toner concentration of 1%, whereupon the quantity of charge imparted was measured by a blow off method and found to be +48 ⁇ C/g.
- Example 27 The operation was conducted in the same manner as in Example 27 except that compound (29) was used instead of compound (12) as the charge-controlling agent, whereupon the quantity of charge imparted was measured and found to be +40 ⁇ C/g.
- the electrostatic image-developing toner containing a compound having a specific structure of the present invention is superior in the electric charge characteristics to conventional toners, and it is an electrostatic image-developing toner of high quality, which does not bring about e.g. copy staining even by continuous copying operation.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
An electrostatic image-developing toner comprising at least a resin and a colorant, which contains at least one member selected from the group consisting of compounds of the following formulas (I) and (II): ##STR1## wherein each of R1, R2, Ar1 and Ar2 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, and A is (B) (SO3.sup.⊖)2 or MX6 2⊖, wherein B is ##STR2## (wherein each of R3 and R4 is a hydrogen atom, an alkyl group, a hydroxyl group or an amino group), M is a titanium atom, a zirconium atom or a silicon atom, and X is a fluorine atom, a chlorine atom or a bromine atom.
Description
The present invention relates to an electrostatic image-developing toner useful for e.g. electrophotographic copying machines.
In its developing step, a developer useful for e.g. electrophotographic copying machines, is first deposited on an image support such as a photoreceptor having an electrostatic image formed thereon. Then, it is transferred in a transfer step from the photoreceptor to a transfer paper and then fixed on a copy sheet in a fixing step. As the developer for developing an electrostatic image formed on a latent image-maintaining surface, a two component developer comprising a carrier and a toner, and an one component developer (a magnetic toner) which requires no carrier, are known for this purpose.
Further, as an agent for imparting electric charge to a developer, a Nigrosine dye, a charge controlling agent such as a quaternary ammonium salt or a coating agent for carrier, has been known. For example, Japanese Unexamined Patent Publications No. 119364/1982 (which corresponds to U.S. Pat. No. 4,338,390), No. 169857/1985 and No. 54/1989 (which corresponds to EP 284000A) disclose quaternary ammonium salts as charge controlling agents.
However, these conventional charge-imparting agents are not necessarily adequate in their charge-imparting effects and have a problem that the charge-imparting effects tends to change with time and copy staining tends to result by continuous copying, whereby the copying quality tends to deteriorate.
Under these circumstances, the present inventors have conducted extensive researches to present an electrostatic image-developing toner of high quality which is less likely to bring about copy staining even when time passes. As a result, they have found it possible to solve such problems by incorporating a compound having a certain specific structure into the toner. The present invention has been accomplished on the basis of this discovery.
Namely, the present invention provides an electrostatic image-developing toner comprising at least a resin and a colorant, which contains at least one member selected from the group consisting of compounds of the following formulas (I) and (II): ##STR3## wherein each of R1, R2, Ar1 and Ar2 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, and A is (B)(SO3.sup.⊖)2 or MX6 2⊖,
wherein B is ##STR4## (wherein each of R3 and R4 is a hydrogen atom, an alkyl group, a hydroxyl group or an amino group), M is a titanium atom, a zirconium atom or a silicon atom, and X is a fluorine atom, a chlorine atom or a bromine atom.
The accompanying drawing, FIG. 1 is a graph showing the relation between the amount of a charge-controlling agent incorporated and the quantity of charge imparted to a toner, wherein symbol represents Example 25, symbol □ represents Example 26, and represents Comparative Example 2.
Now, the present invention will be described in detail with reference to the preferred embodiments.
The electrostatic image-developing toner of the present invention is characterized in that it contains at least one member selected from the group consisting of compounds of the above formulas (I) and (II).
In the formula (II), ##STR5## represents ##STR6## Accordingly ##STR7## represents ##STR8## The same applies hereinafter.
Specifically, each of R1 and R2 may be an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group; an aralkyl group such as a benzyl group; or a substituted aralkyl group such as a lower alkyl-substituted benzyl group, a nitro-substituted benzyl group or a halogen-substituted benzyl group. Among them, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group or a substituted benzyl group is preferred. The sum of the carbon members of R1 and R2 is preferably at least 13, more preferably at least 19, most preferably at least 30.
Each of Ar1 and Ar2 which are independent from each other, is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group; an aralkyl group such as a benzyl group; or a substituted aralkyl group such as a lower alkyl-substituted benzyl group, a nitro-substituted benzyl group or a halogen-substituted benzyl group. Particularly preferred is a heptyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group or a substituted benzyl group. The sum of the carbon numbers of Ar1 and Ar2 is preferably at least 13, more preferably at least 19, and most preferably at least 30.
Each of R3 and R4 is a hydrogen atom, an alkyl group, a hydroxyl group or an amino group. Particularly preferred is a hydrogen atom, a hydroxyl group or an amino group.
M is a titanium atom, a zirconium atom or a silicon atom. Particularly preferred is a titanium atom or a zirconium atom. X is a fluorine atom, a chlorine atom or a bromine atom. Particularly preferred is a fluorine atom.
Compounds having the following structural formulas may be mentioned as specific examples of the compounds of the formulas (I) and (II) suitable for incorporation to the electrostatic image-developing toner of the present invention. However, compounds of the formulas (I) and (II) useful in the present invention are not limited to such specific examples.
A compound of the formula (I) or (II) can be used for the present invention irrespective of the process for its production. However, an example of a specific process will be described below.
The compound of the formula (I) can usually be obtained by reacting e.g. a halogenated quaternary ammonium salt of the following formula (IV): ##STR11## wherein R1 and R2 are as defined above with respect to the formula (I), and Z.sup.⊖ is a halogen atom such as chlorine or bromine, with a compound of the following formula (V) or (VI) in water or in an alcohol under heating to a temperature of about 70° C.
(B)(SO.sub.3 Y).sub.2 (V)
Y.sub.2 MX.sub.6 (VI)
wherein B, M and X are as defined above with respect to the formula (I), and Y is an alkali metal such as sodium or potassium.
The cation component in the formula (II) can be prepared usually by reacting e.g. a halogenated compound of the following formula (VII):
Ar'Y (VII)
wherein Ar' is the same as Ar1 and Ar2 in the formula (II), and Y is a halogen atom such as chlorine or bromine, with triethylenediamine in an organic solvent inert to the reaction such as a dimethyl formamide or N-methylpyrrolidone under heating to a temperature of about 70° C. for a period of e.g. 24 hours.
The resin for the toner of the present invention may be selected from a wide range including known resins. For example, a styrene resin (a homopolymer or a copolymer of styrene or a substituted styrene) such as polystyrene, chloropolystyrene, poly-α-methyl styrene, a styrene-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-butadiene copolymer, a styrene-vinyl chloride copolymer, a styrene-vinyl acetate copolymer, a styrene-maleic acid copolymer, a styrene-acrylate copolymer (such as a styrene-methyl acrylate copolymer, a styrene-ethyl acrylate copolymer, a styrene-butyl acrylate copolymer, a styrene-octyl acrylate copolymer or a styrene-phenyl acrylate copolymer), a styrene-methacrylate copolymer (such as styrene-methyl methacrylate copolymer, a styrene-ethyl methacrylate copolymer, a styrene-butyl methacrylate copolymer or a styrene-phenyl methacrylate copolymer), a styrene-methyl α-chloroacrylate copolymer, or a styrene-acrylonitrileacrylate copolymer, a vinylchloride resin, a rosin-modified maleic acid resin, a phenol resin, an epoxy resin, a polyester resin, a low molecular weight polyethylene, a low molecular weight polypropylene, an ionomer resin, a polyurethane resin, a silicone resin, a ketone resin, an ethylene-ethyl acrylate copolymer, a xylene resin, or a polyvinyl butyral resin, may be mentioned. Particularly preferred as the resin to be used in the present invention, is a styrene-acrylate copolymer, a styrene-methacrylate copolymer, a saturated or unsaturated polyester resin or an epoxy resin.
These resins may be used alone or in combination as a mixture of two or more of them.
The content of the compound of the formula (I) or (II) in the toner is preferably from 0.1 to 20 parts by weight, more preferably from 0.2 to 10 parts by weight, per 100 parts by weight of the resin.
If the content of the compound the formula (I) or (II) is too small, no adequate effects for improving the electric charge will be obtained. On the other hand, if the content is too large, the quality of the toner tends to deteriorate, such being undesirable.
The colorant to be used in the present invention is not particularly limited so long as it is the one which has been commonly employed. To obtain a black color toner, carbon black may, for example, be used. The compound of the formula (I) or (II) is usually white and thus may be incorporated to a colored toner such as a blue, red or yellow toner. In such a case, a colorant composed of a dye or pigment having the corresponding color, is employed.
The content of the colorant is preferably from 3 to 20 parts by weight, per 100 parts by weight of resin.
Further, in addition to the compound of the formula (I) or (II), other charge-controlling agents including known agents such as Nigrosine dyes, quaternary ammonium salts and polyamine resins may be incorporated to the toner of the present invention.
Further, an additive such as a low molecular weight olefine polymer or fine powder silica may be incorporated in order to improve the fixing property or flowability, as a constituting component of the toner of the present invention.
The toner may be prepared by a method which comprises kneading the above mentioned respective components by e.g. a kneader, followed, by, cooling, and then by pulverization and classification. The toner of the present invention may be applied not only to a two component developer but also to a so-called one component developer (a magnetic toner) such as a capsulated toner, a polymer toner or a magnetite-containing toner.
The average particle size of the toner is preferably from 5 to 20 μm. There is no particular restriction as to the carrier to be mixed with the toner of the present invention to form a developer. However, such a carrier is preferably a ferrite or magnetite carrier having an average particle size of from 10 to 200 μm. Further, there is no particular restriction as to the particle size. In such a case, a so-called coating carrier having a fluorine resin coated for the purpose of improving the durability for continuous use, may also be used. Further, other known carriers including iron powder, may also be employed. Such a carrier is used preferably in an amount of from 5 to 100 parts by weight per part by weight of the toner.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples. In the following Examples, "parts" means "parts by weight" unless otherwise specified.
______________________________________
Styrene resin (SBM-600, tradename,
100 parts
manufactured by Sanyo Kasei K.K.)
Carbon black (#44, manufactured
10 parts
by Mitusbishi Kasei Corporation)
Compound (1) 2 parts
______________________________________
The above materials were blended and kneaded, followed by pulverization and classification to obtain a black toner having an average particle size of 11 μm.
Five parts of this toner and 100 parts of a fluorine resin-coating carrier having an average particle size of about 100 μm were mixed and stirred to obtain a developer. Then, using this developer, a copy was taken by a copying machine employing an organic photoconductor as a photoreceptor, whereby a clear copy free from so-called fogging, i.e. free from a stain on a blank portion, was obtained.
In each Example, the operation was conducted in the same manner as in Example 1 except that a compound specified in the following Table 1 was used in an amount specified in Table 1 instead of 2 parts of compound (1), whereby a clear copy was obtained as in Example 1.
A developer was prepared in the same manner as in Example 1 except that compound (1) was not used as the material, and it was used for copying, whereby a copy of poor copy quality with substantial fogging was obtained.
TABLE 1
______________________________________
Compund No.
Parts
______________________________________
Example 2 (5) 2
Example 3 (8) 3
Example 4 (12) 2
Example 5 (16) 2
Example 6 (18) 2
Example 7 (23) 2
Example 8 (24) 3
Example 9 (29) 2
Example 10 (30) 2
Example 11 (31) 2
Example 12 (32) 5
Example 13 (33) 4
Example 14 (34) 6
Example 15 (36) 2
Example 16 (39) 5
Example 17 (43) 4
Example 18 (44) 6
Example 19 (46) 3
Example 20 (49) 3
Example 21 (50) 2
Example 22 (62) 3
Example 23 (65) 3
Example 24 (66) 2
______________________________________
______________________________________
Styrene-acrylate resin (G-10, tradename,
100 parts
manufactured by Nipppon Carbide K.K.)
Carbon black (MA-100, tradename, manufactured
6 parts
by Mitsubishi Kasei Corporation)
______________________________________
To the above materials, compound (12) was blended and kneaded in an amount of 0.5 part, 1 part or 2 parts, followed by pulverization and classification to obtain a black toner having an average particle size of 10 μm.
Then, 3.5 parts of this toner and 100 parts of a silicone resin-coating ferrite carrier having an average particle size of about 100 μm were mixed to obtain a two component developer, and the quantity of charge imparted was measured by a blow off method, whereby the characteristic as shown in FIG. 1 was obtained.
A developer was prepared in the same manner as in Example 25 except that compound (29) was used instead of compound (12) as the charge-controlling agent, and the quantity of charge imparted thereto was measured by a blow off method, whereby the characteristic as shown in FIG. 1 was obtained.
A developer was prepared in the same manner as in Example 25 except that compound (A) ##STR12## was used instead of compound (12), and the quantity of charge imparted thereto was measured by a blow off method, whereby the characteristic as shown in FIG. 1 was obtained.
To 100 parts of a styrene acrylate resin (SA-302, tradename, Nippon Carbide K.K.), 1 part of compound (12) was mixed by a mixer to let it deposit on the polymer surface to obtain a pseudo-toner. This pseudo-toner was shaken with an iron powder carrier for 30 minutes at a toner concentration of 1%, whereupon the quantity of charge imparted was measured by a blow off method and found to be +48 μC/g.
The operation was conducted in the same manner as in Example 27 except that compound (29) was used instead of compound (12) as the charge-controlling agent, whereupon the quantity of charge imparted was measured and found to be +40 μC/g.
The operation was conducted in the same manner as in Example 27 except that compound (B) (C16 H33 --2 N.sup.⊕ (CH3)2.1/4[MO8 O26 ]4⊕ was used instead of compound (12) as the charge-controlling agent, whereupon the quantity of charge imparted was measured and found to be +18 μC/g.
The operation was conducted in the same manner as in Example 27 except that compound (A) ##STR13## was used instead of compound (12) as the charge-controlling agent, whereupon the quantity of charge imparted was measured and found to be +18 μC/g.
The electrostatic image-developing toner containing a compound having a specific structure of the present invention, is superior in the electric charge characteristics to conventional toners, and it is an electrostatic image-developing toner of high quality, which does not bring about e.g. copy staining even by continuous copying operation.
Claims (15)
1. An electrostatic image-developing toner comprising at least a resin and a colorant, and contains at least one member selected from the group consisting of compounds of formulas (I) and (II): ##STR14## wherein each of R1, R2, Ar1 and Ar2 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, and A is (B)(SO3.sup.⊖)2 or MX6 2⊖,
wherein B is ##STR15## wherein each of R3 and R4 is a hydrogen atom, an alkyl group, a hydroxyl group or an amino group, M is a titanium atom, a zirconium atom or a silicon atom, and X is a fluorine atom, a chlorine atom or a bromine atom.
2. The electrostatic image-developing toner according to claim 1, wherein A is (B)(SO3.sup.⊖)2.
3. The electrostatic image-developing toner according to claim 2, wherein B is ##STR16## .
4. The electrostatic image-developing toner according to claim 3, wherein R3 or R4 is a hydrogen atom, an amino group or a hydroxyl group.
5. The electrostatic image-developing toner according to claim 3, wherein A is 1,5-naphthalenedisulfonate.
6. The electrostatic image-developing toner according to claim 1, wherein A is MX6 2⊕.
7. The electrostatic image-developing toner according to claim 6, wherein M is a titanium atom or a zirconium atom, and X is a fluorine atom.
8. The electrostatic image-developing toner according to claim 6, wherein M is a zirconium atom, and X is a fluorine atom.
9. The electrostatic image-developing toner according to claim 1, wherein said at least one member is present in an amount of from 0.1 to 20 parts by weight per 100 parts by weight of the resin.
10. The electrostatic image-developing toner according to claim 1, wherein the resin is a styrene resin or a styrene-acrylate copolymer resin.
11. The electrostatic image-developing toner according to claim 1, wherein each of R1, R2, Ar1 and Ar2 is a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a benzyl group, a lower alkyl-substituted benzyl group, a nitro-substituted benzyl group and a halogen-substituted benzyl group.
12. The electrostatic image-developing toner according to claim 1, wherein at least one of R1 and R2, and at least one of Ar1 and Ar2, are substituents selected from the group consisting of a heptyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, a octadecyl group, a benzyl group, a lower alkyl-substituted benzyl group, a nitro-substituted benzyl group and a halogen-substituted benzyl group.
13. The electrostatic image-developing toner according to claim 1, wherein the sum of the carbon numbers of R1 and R2, and the sum of the carbon numbers of Ar1 and Ar2, are at least 13, respectively.
14. The electrostatic image-developing toner according to claim 1, wherein the sum of the carbon numbers of R1 and R2, and the sum of the carbon numbers of Ar1 and Ar2, are at least 19, respectively.
15. The electrostatic image-developing toner according to claim 1, wherein the sum of the carbon numbers of R1 and R2, and the sum of the carbon numbers of Ar1 and Ar2, are at least 30, respectively.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24204390 | 1990-09-12 | ||
| JP2-242043 | 1990-09-12 | ||
| JP2-402016 | 1990-12-13 | ||
| JP2402016A JP2976527B2 (en) | 1990-09-12 | 1990-12-13 | Toner for developing electrostatic images |
| JP3-071236 | 1991-04-03 | ||
| JP3071236A JPH04306665A (en) | 1991-04-03 | 1991-04-03 | Tonner for electrostatic charge image development |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5166030A true US5166030A (en) | 1992-11-24 |
Family
ID=27300592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/757,211 Expired - Lifetime US5166030A (en) | 1990-09-12 | 1991-09-10 | Electrostatic image-developing toner containing a quaternary ammonium charge controlling agent |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5166030A (en) |
| EP (1) | EP0475263B1 (en) |
| AU (1) | AU8379691A (en) |
| CA (1) | CA2051162A1 (en) |
| DE (1) | DE69125899T2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5545502A (en) * | 1992-12-14 | 1996-08-13 | Mitsubishi Chemical Corporation | Electrostatic image-developing toner |
| US5604069A (en) * | 1994-12-07 | 1997-02-18 | Eastman Kodak Company | Toners and developers containing ammonium trihalozincates as charge-control agents |
| US5616444A (en) * | 1994-12-07 | 1997-04-01 | Eastman Kodak Company | Toners and developers containing BIS(ammonium) tetrahalocuprate salts as charge-control agents |
| EP1035448A1 (en) * | 1999-03-05 | 2000-09-13 | Hodogaya Chemical Co Ltd | Electrostatic image developing toner employing a metal complex |
| US20090068581A1 (en) * | 2007-09-07 | 2009-03-12 | Kusaka Natsuko | Magenta Toner for Developing Electrostatic Image |
| CN102408753A (en) * | 2010-09-15 | 2012-04-11 | Jsr株式会社 | Alkaline colorant, colored composition, color filter and display element |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304449A (en) * | 1992-11-30 | 1994-04-19 | Xerox Corporation | Toner and developer compositions with pyridinium compounds and tetrasubstituted ammonium salts as charge enhancing additives |
| US5582946A (en) * | 1994-12-07 | 1996-12-10 | Eastman Kodak Company | Toners and developers containing bis(ammonium) tetrahalomanganate salts as charge-control agents |
| CN106117217B (en) * | 2016-06-08 | 2018-07-10 | 南京远淑医药科技有限公司 | A kind of preparation method of fluozirconate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2359440A1 (en) * | 1976-07-21 | 1978-02-17 | Eastman Kodak Co | DRY ELECTOGRAPHIC DEVELOPER AND DEVELOPER THE CONTAINER |
| EP0242420A1 (en) * | 1985-10-21 | 1987-10-28 | Orient Chemical Industries, Ltd. | A toner for developing electrostatic latent images and a use thereof |
| EP0321363A2 (en) * | 1987-12-17 | 1989-06-21 | EASTMAN KODAK COMPANY (a New Jersey corporation) | New electrostatographic toners and developers containing new charge-control agents |
| US4937157A (en) * | 1989-08-21 | 1990-06-26 | Xerox Corporation | Toner and developer compositions with charge enhancing additives |
| US4965158A (en) * | 1986-08-01 | 1990-10-23 | Xerox Corporation | Toner compositions with modified charge enhancing additives |
| US4980258A (en) * | 1988-11-17 | 1990-12-25 | Ricoh Company, Ltd. | Dry type developer for electrophotography |
-
1991
- 1991-09-04 EP EP91114929A patent/EP0475263B1/en not_active Expired - Lifetime
- 1991-09-04 DE DE69125899T patent/DE69125899T2/en not_active Expired - Fee Related
- 1991-09-10 US US07/757,211 patent/US5166030A/en not_active Expired - Lifetime
- 1991-09-10 AU AU83796/91A patent/AU8379691A/en not_active Abandoned
- 1991-09-11 CA CA002051162A patent/CA2051162A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2359440A1 (en) * | 1976-07-21 | 1978-02-17 | Eastman Kodak Co | DRY ELECTOGRAPHIC DEVELOPER AND DEVELOPER THE CONTAINER |
| EP0242420A1 (en) * | 1985-10-21 | 1987-10-28 | Orient Chemical Industries, Ltd. | A toner for developing electrostatic latent images and a use thereof |
| US4965158A (en) * | 1986-08-01 | 1990-10-23 | Xerox Corporation | Toner compositions with modified charge enhancing additives |
| EP0321363A2 (en) * | 1987-12-17 | 1989-06-21 | EASTMAN KODAK COMPANY (a New Jersey corporation) | New electrostatographic toners and developers containing new charge-control agents |
| US4980258A (en) * | 1988-11-17 | 1990-12-25 | Ricoh Company, Ltd. | Dry type developer for electrophotography |
| US4937157A (en) * | 1989-08-21 | 1990-06-26 | Xerox Corporation | Toner and developer compositions with charge enhancing additives |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5545502A (en) * | 1992-12-14 | 1996-08-13 | Mitsubishi Chemical Corporation | Electrostatic image-developing toner |
| US5604069A (en) * | 1994-12-07 | 1997-02-18 | Eastman Kodak Company | Toners and developers containing ammonium trihalozincates as charge-control agents |
| US5616444A (en) * | 1994-12-07 | 1997-04-01 | Eastman Kodak Company | Toners and developers containing BIS(ammonium) tetrahalocuprate salts as charge-control agents |
| EP1035448A1 (en) * | 1999-03-05 | 2000-09-13 | Hodogaya Chemical Co Ltd | Electrostatic image developing toner employing a metal complex |
| US20090068581A1 (en) * | 2007-09-07 | 2009-03-12 | Kusaka Natsuko | Magenta Toner for Developing Electrostatic Image |
| US8247145B2 (en) * | 2007-09-07 | 2012-08-21 | Konica Minolta Business Technologies, Inc. | Magenta toner for developing electrostatic image |
| CN101382746B (en) * | 2007-09-07 | 2013-06-05 | 柯尼卡美能达商用科技株式会社 | Magenta toner for developing electrostatic image |
| CN102408753A (en) * | 2010-09-15 | 2012-04-11 | Jsr株式会社 | Alkaline colorant, colored composition, color filter and display element |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69125899D1 (en) | 1997-06-05 |
| DE69125899T2 (en) | 1997-09-04 |
| EP0475263B1 (en) | 1997-05-02 |
| AU8379691A (en) | 1992-03-19 |
| EP0475263A1 (en) | 1992-03-18 |
| CA2051162A1 (en) | 1992-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5200288A (en) | Electrostatic developing toner with hydroxyaromatic carboxylic acid additive | |
| US4812381A (en) | Electrostatographic toners and developers containing new charge-control agents | |
| US4590139A (en) | Three color toner kit and method of use | |
| US5166030A (en) | Electrostatic image-developing toner containing a quaternary ammonium charge controlling agent | |
| US5413891A (en) | Electrostatic image developing toner | |
| KR930006193B1 (en) | Quaternary ammonium salt and electro photographischer toner | |
| US4789614A (en) | Toners and developers containing benzyldimethylalkylammonium charge-control agents | |
| US4834921A (en) | Quaternary ammonium salts | |
| US5721084A (en) | Charge controlling agent for electrostatic image development, and toner and charge-imparting material employing it | |
| US5407774A (en) | Charge control agent and positively chargeable toner for developing electrostatic images | |
| JPH07234544A (en) | Toner for electrostatic image development | |
| US4851561A (en) | Quaternary ammonium salts | |
| EP0548772B1 (en) | Toner for the development of electrostatic images | |
| US4803017A (en) | Quaternary ammonium salts | |
| US5232809A (en) | Toner for electrophotography | |
| US4812380A (en) | Electrostatographic toners and developers containing new charge-control agents | |
| JPH04107569A (en) | Electrophotographic toner | |
| US5061589A (en) | Toner for electrophotography | |
| US5679489A (en) | Electrostatic image developing toner | |
| US4806284A (en) | New quaternary ammonium salts | |
| US5391454A (en) | Electrostatic image developing toner | |
| JP2907564B2 (en) | Electrophotographic toner | |
| KR100419765B1 (en) | Electrostatic toner | |
| US4812382A (en) | Electrostatographic toners and developers containing new charge-control agents | |
| US5378573A (en) | Electrophotographic toner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: MITSUBISHI KASEI CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ONO, HITOSHI;ANDO, OSAMU;TAKEUCHI, MASAKO;REEL/FRAME:005838/0826 Effective date: 19910823 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| REMI | Maintenance fee reminder mailed | ||
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| FPAY | Fee payment |
Year of fee payment: 12 |